Multi-layer golf ball

ABSTRACT

Golf balls consisting of a dual core and a dual cover are disclosed. The surface hardness of the outer core layer is greater than the material hardness of the inner cover layer, and is preferably 75 Shore C or greater.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/048,021, filed Mar. 13, 2008, which is a continuation-in-part of U.S.patent application Ser. No. 11/767,070, filed Jun. 22, 2007, nowabandoned, which is a continuation-in-part of U.S. patent applicationSer. No. 10/773,906, filed Feb. 6, 2004, now U.S. Pat. No. 7,255,656,which is a continuation-in-part of U.S. patent application Ser. No.10/341,574, filed Jan. 13, 2003, now U.S. Pat. No. 6,852,044, which is acontinuation-in-part of U.S. patent application Ser. No. 10/002,641,filed Nov. 28, 2001, now U.S. Pat. No. 6,547,677, the entire disclosuresof which are hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to golf balls, and moreparticularly to golf balls having dual cores surrounded by dual covers,wherein the surface hardness of the outer core layer is greater than thematerial hardness of the inner cover layer.

BACKGROUND OF THE INVENTION

Numerous golf balls having a multilayer construction wherein the corehardness and cover hardness have been variously improved are disclosedin the prior art. For example, U.S. Pat. No. 6,987,159 to Iwamidiscloses a solid golf ball with a solid core and a polyurethane cover,wherein the difference in Shore D hardness between a center portion anda surface portion of the solid core is at least 15, the polyurethanecover has a thickness (t) of not more than 1.0 mm and is formed from acured urethane composition having a Shore D hardness (D) of from 35 to60, and a product of t and D ranges from 10 to 45.

U.S. Pat. No. 7,175,542 to Watanabe et al. discloses a multi-piece solidgolf ball composed of a multilayer core having at least an inner corelayer and an outer core layer, one or more cover layers which enclosethe core, and numerous dimples formed on a surface of the cover layer.The golf ball is characterized in that the following hardness conditionsare satisfied: (1) (JIS-C hardness of cover)−(JIS-C hardness at centerof core)≧27, (2) 23≦(JIS-C hardness at surface of core)−(JIS-C hardnessat center of core)≦40, and (3) 0.50≦[(deflection amount of entirecore)/(deflection amount of inner core layer)]≦0.75.

U.S. Pat. No. 6,679,791 to Watanabe discloses a multi-piece golf ballwhich includes a rubbery elastic core, a cover having a plurality ofdimples on the surface thereof, and at least one intermediate layerbetween the core and the cover. The intermediate layer is composed of aresin material which is harder than the cover. The elastic core has ahardness which gradually increases radially outward from the center tothe surface thereof. The center and surface of the elastic core have ahardness difference of at least 18 JIS-C hardness units.

U.S. Pat. No. 5,782,707 to Yamagishi et al. discloses a three-piecesolid golf ball consisting of a solid core, an intermediate layer, and acover, wherein the hardness is measured by a JIS-C scale hardness meter,the core center hardness is up to 75 degrees, the core surface hardnessis up to 85 degrees, the core surface hardness is higher than the corecenter hardness by 8 to 20 degrees, the intermediate layer hardness ishigher than the core surface hardness by at least 5 degrees, and thecover hardness is lower than the intermediate layer hardness by at least5 degrees.

Additional examples can be found, for example, in U.S. Pat. No.6,686,436 to Iwami, U.S. Pat. No. 6,786,836 to Higuchi et al., U.S. Pat.No. 7,153,224 to Higuchi et al., and U.S. Pat. No. 7,226,367 to Higuchiet al.

The present invention provides a novel multilayer golf ball constructionwhich may provide one or more of the following benefits: higher spin onfull iron shots due and superior overall ball performance properties.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to a golf ballconsisting of a center, an outer core layer core, an inner cover layer,and an outer cover layer. The center is formed from a first rubbercomposition and has a diameter of from 0.75 inches to 1.19 inches and acenter hardness of 50 Shore C or greater. The outer core layer is formedfrom a second rubber composition and has a surface hardness of 75 ShoreC or greater. The inner cover layer is formed from a thermoplasticcomposition and has a material hardness less than the surface hardnessof the outer core layer. The outer cover layer is formed from apolyurethane or polyurea composition.

In another embodiment, the present invention is directed to a golf ballconsisting of a center, an outer core layer core, an inner cover layer,and an outer cover layer. The center is formed from a first rubbercomposition and has a diameter of from 0.75 inches to 1.19 inches, acenter hardness of from 50 Shore C to 70 Shore C, and a surface hardnessof from 60 Shore C to 85 Shore C. The surface hardness of the center isat least 10 Shore C units greater than the center hardness. The outercore layer is formed from a second rubber composition and has a surfacehardness of from 80 Shore C to 95 Shore C. The surface hardness of theouter core layer is at least 20 Shore C units greater than the centerhardness. The inner cover layer is formed from a thermoplasticcomposition and has a material hardness of less than 95 Shore C. Theouter cover layer is formed from a polyurethane or polyurea composition.The surface hardness of the outer core layer is greater than thematerial hardness of the inner cover layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a golf ball according to oneembodiment of the present invention.

DETAILED DESCRIPTION

FIG. 1 shows a golf ball 30 according to one embodiment of the presentinvention, including a center 32, an outer core layer 34, an inner coverlayer 36, and an outer cover layer 38.

A golf ball having a dual core (i.e., two-layer core) and a dual cover(i.e., two-layer cover) enclosing the core is disclosed. The dual coreconsists of a center and an outer core layer. The center has a diameterwithin a range having a lower limit of 0.75 or 0.85 or 0.875 inches andan upper limit of 1.125 or 1.15 or 1.19 inches. The outer core layerencloses the center such that the two-layer core has an overall diameterwithin a range having a lower limit of 1.40 or 1.50 or 1.51 or 1.52 or1.525 inches and an upper limit of 1.54 or 1.55 or 1.555 or 1.56 or 1.59inches.

Preferably, the center has a center hardness of 50 Shore C or greater,or 55 Shore C or greater, or 60 Shore C or greater, or a center hardnesswithin a range having a lower limit of 50 or 55 or 60 Shore C and anupper limit of 65 or 70 or 80 Shore C. The center preferably has asurface hardness of 65 Shore C or greater, or 70 Shore C or greater, ora surface hardness within a range having a lower limit of 55 or 60 or 65or 70 Shore C or 75 Shore C and an upper limit of 80 or 85 Shore C. Theouter core layer preferably has a surface hardness of 75 Shore C orgreater, or 80 Shore C or greater, or greater than 80 Shore C, or 85Shore C or greater, or greater than 85 Shore C, or 87 Shore C orgreater, or greater than 87 Shore C, or 89 Shore C or greater, orgreater than 89 Shore C, or 90 Shore C or greater, or greater than 90Shore C, or a surface hardness within a range having a lower limit of 75or 80 or 85 Shore C and an upper limit of 90 or 95 Shore C.

In a particular embodiment, the surface hardness of the center isgreater than or equal to the center hardness of the center. In anotherparticular embodiment, the center has a positive hardness gradientwherein the surface hardness of the center is at least 10 Shore C unitsgreater than the center hardness of the center.

In a particular embodiment, the surface hardness of the outer core layeris greater than or equal to the surface hardness and center hardness ofthe center. In another particular embodiment, the core has a positivehardness gradient wherein the surface hardness of the outer core layeris at least 20 Shore C units, or at least 25 Shore C units greater, orat least 30 units greater, than the center hardness of the center.

The surface hardness of a center or outer core layer is obtained fromthe average of a number of measurements taken from opposing hemispheresof a core, taking care to avoid making measurements on the parting lineof the core or on surface defects, such as holes or protrusions.Hardness measurements are made pursuant to ASTM D-2240 “IndentationHardness of Rubber and Plastic by Means of a Durometer.” Because of thecurved surface of a core, care must be taken to insure that the core iscentered under the durometer indentor before a surface hardness readingis obtained. A calibrated, digital durometer, capable of reading to 0.1hardness units is used for all hardness measurements and is set to takehardness readings at 1 second after the maximum reading is obtained. Thedigital durometer must be attached to, and its foot made parallel to,the base of an automatic stand, such that the weight on the durometerand attack rate conform to ASTM D-2240.

The center hardness of the core is obtained according to the followingprocedure. The core is gently pressed into a hemispherical holder havingan internal diameter approximately slightly smaller than the diameter ofthe core, such that the core is held in place in the hemisphericalportion of the holder while concurrently leaving the geometric centralplane of the core exposed. The core is secured in the holder byfriction, such that it will not move during the cutting and grindingsteps, but the friction is not so excessive that distortion of thenatural shape of the core would result. The core is secured such thatthe parting line of the core is roughly parallel to the top of theholder. The diameter of the core is measured 90 degrees to thisorientation prior to securing. A measurement is also made from thebottom of the holder to the top of the core to provide a reference pointfor future calculations. A rough cut, made slightly above the exposedgeometric center of the core using a band saw or other appropriatecutting tool, making sure that the core does not move in the holderduring this step. The remainder of the core, still in the holder, issecured to the base plate of a surface grinding machine. The exposed‘rough’ surface is ground to a smooth, flat surface, revealing thegeometric center of the core, which can be verified by measuring theheight of the bottom of the holder to the exposed surface of the core,making sure that exactly half of the original height of the core, asmeasured above, has been removed to within ±0.004 inches. Leaving thecore in the holder, the center of the core is found with a center squareand carefully marked and the hardness is measured at the center mark.

The center is preferably formed from a rubber composition or from ahighly resilient thermoplastic polymer such as a highly neutralizedpolymer (“HNP”) composition. Particularly suitable thermoplasticpolymers include Surlyn® ionomers, Hytrel® thermoplastic polyesterelastomers, and ionomeric materials sold under the trade names DuPont®HPF 1000 and DuPont® HPF 2000, all of which are commercially availablefrom E. I. du Pont de Nemours and Company; Iotek® ionomers, commerciallyavailable from ExxonMobil Chemical Company; and Pebax® thermoplasticpolyether block amides, commercially available from Arkema Inc.

Suitable HNP compositions for use in forming the center comprise an HNPand optionally additives, fillers, and/or melt flow modifiers. SuitableHNPs are salts of homopolymers and copolymers of α,β-ethylenicallyunsaturated mono- or dicarboxylic acids, and combinations thereof,optionally including a softening monomer. The acid polymer isneutralized to 70% or higher, including up to 100%, with a suitablecation source. Suitable additives and fillers include, for example,blowing and foaming agents, optical brighteners, coloring agents,fluorescent agents, whitening agents, UV absorbers, light stabilizers,defoaming agents, processing aids, mica, talc, nanofillers,antioxidants, stabilizers, softening agents, fragrance components,plasticizers, impact modifiers, acid copolymer wax, surfactants;inorganic fillers, such as zinc oxide, titanium dioxide, tin oxide,calcium oxide, magnesium oxide, barium sulfate, zinc sulfate, calciumcarbonate, zinc carbonate, barium carbonate, mica, talc, clay, silica,lead silicate, and the like; high specific gravity metal powder fillers,such as tungsten powder, molybdenum powder, and the like; regrind, i.e.,core material that is ground and recycled; and nano-fillers. Suitablemelt flow modifiers include, for example, fatty acids and salts thereof,polyamides, polyesters, polyacrylates, polyurethanes, polyethers,polyureas, polyhydric alcohols, and combinations thereof. Suitable HNPcompositions also include blends of HNPs with partially neutralizedionomers as disclosed, for example, in U.S. Patent ApplicationPublication No. 2006/0128904, the entire disclosure of which is herebyincorporated herein by reference, and blends of HNPs with additionalthermoplastic and thermoset materials, including, but not limited to,ionomers, acid copolymers, engineering thermoplastics, fattyacid/salt-based highly neutralized polymers, polybutadienes,polyurethanes, polyesters, thermoplastic elastomers, and otherconventional polymeric materials. Particularly suitable as a core layermaterial is DuPont® HPF 1000, commercially available from E. I. du Pontde Nemours and Company. Suitable HNP compositions are further disclosed,for example, in U.S. Pat. Nos. 6,653,382, 6,756,436, 6,777,472,6,894,098, 6,919,393, and 6,953,820, the entire disclosures of which arehereby incorporated herein by reference.

Suitable rubber compositions for use in forming the center comprise abase rubber, a crosslinking agent, a filler, and a co-crosslinking orinitiator agent. Typical base rubber materials include natural andsynthetic rubbers, and combinations of two or more thereof. The baserubber is preferably polybutadiene or a mixture of polybutadiene withother elastomers. Particularly preferred is 1,4-polybutadiene having acis-structure of at least 40%. More preferably, the base rubber is ahigh-Mooney-viscosity rubber. Lesser amounts of other thermosetmaterials may be incorporated into the base rubber. Such materialsinclude, for example, cis-polyisoprene, trans-polyisoprene, balata,polychloroprene, polynorbornene, polyoctenamer, polypentenamer, butylrubber, EPR, EPDM, styrene-butadiene, and similar thermoset materials.The crosslinking agent typically includes a metal salt, such as a zinc-,aluminum-, sodium-, lithium-, nickel-, calcium-, or magnesium-salt, ofan unsaturated fatty acid or monocarboxylic acid, such as (meth)acrylicacid. Preferred crosslinking agents include zinc acrylate, zincdiacrylate (ZDA), zinc methacrylate, and zinc dimethacrylate (ZDMA), andmixtures thereof. The crosslinking agent must be present in an amountsufficient to crosslink a portion of the chains of the polymers in theresilient polymer component. The crosslinking agent is generally presentin the rubber composition in an amount of from 15 to 30 phr, or from 19to 25 phr, or from 20 to 24 phr. The desired compression may be obtainedby adjusting the amount of crosslinking, which can be achieved, forexample, by altering the type and amount of crosslinking agent. Theinitiator agent can be any known polymerization initiator whichdecomposes during the cure cycle, including, but not limited to, dicumylperoxide, 1,1-di-(t-butylperoxy) 3,3,5-trimethyl cyclohexane, a-abis-(t-butylperoxy)diisopropylbenzene,2,5-di-(t-butylperoxy)-2,5-dimethyl hexane, di-t-butyl peroxide,n-butyl-4,4-bis(t-butylperoxy)valerate, lauryl peroxide, benzoylperoxide, t-butyl hydroperoxide, and mixtures thereof.

The rubber composition optionally contains one or more antioxidants.Antioxidants are compounds that can inhibit or prevent the oxidativedegradation of the rubber. Some antioxidants also act as free radicalscavengers; thus, when antioxidants are included in the rubbercomposition, the amount of initiator agent used may be as high or higherthan the amounts disclosed herein. Suitable antioxidants include, forexample, dihydroquinoline antioxidants, amine type antioxidants, andphenolic type antioxidants.

The rubber composition may also contain one or more fillers to adjustthe density and/or specific gravity of the core or cover. Fillers aretypically polymeric or mineral particles. Exemplary fillers includeprecipitated hydrated silica, clay, talc, asbestos, glass fibers, aramidfibers, mica, calcium metasilicate, zinc sulfate, barium sulfate, zincsulfide, lithopone, silicates, silicon carbide, diatomaceous earth,polyvinyl chloride, carbonates (e.g., calcium carbonate, zinc carbonate,barium carbonate, and magnesium carbonate), metals (e.g., titanium,tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper,boron, cobalt, beryllium, zinc, and tin), metal alloys (e.g., steel,brass, bronze, boron carbide whiskers, and tungsten carbide whiskers),oxides (e.g., zinc oxide, tin oxide, iron oxide, calcium oxide, aluminumoxide, titanium dioxide, magnesium oxide, and zirconium oxide),particulate carbonaceous materials (e.g., graphite, carbon black, cottonflock, natural bitumen, cellulose flock, and leather fiber),microballoons (e.g., glass and ceramic), fly ash, regrind (i.e., corematerial that is ground and recycled), nanofillers and combinationsthereof. The amount of particulate material(s) present in the rubbercomposition is typically within a range having a lower limit of 5 partsor 10 parts by weight per 100 parts of the base rubber, and an upperlimit of 30 parts or 50 parts or 100 parts by weight per 100 parts ofthe base rubber. Filler materials may be dual-functional fillers, suchas zinc oxide (which may be used as a filler/acid scavenger) andtitanium dioxide (which may be used as a filler/brightener material).Further examples of suitable fillers and additives include, but are notlimited to, those disclosed in U.S. Patent Application Publication No.2003/0225197, the entire disclosure of which is hereby incorporatedherein by reference.

The rubber composition may also contain one or more additives selectedfrom processing aids, processing oils, plasticizers, coloring agents,fluorescent agents, chemical blowing and foaming agents, defoamingagents, stabilizers, softening agents, impact modifiers, free radicalscavengers, accelerators, scorch retarders, and the like. The amount ofadditive(s) typically present in the rubber composition is typicallywithin a range having a lower limit of 0 parts by weight per 100 partsof the base rubber, and an upper limit of 20 parts or 50 parts or 100parts or 150 parts by weight per 100 parts of the base rubber.

The rubber composition optionally includes a soft and fast agent. Asused herein, “soft and fast agent” means any compound or a blend thereofthat is capable of making a core 1) softer (have a lower compression) ata constant COR and/or 2) faster (have a higher COR at equalcompression), when compared to a core equivalently prepared without asoft and fast agent. Preferably, the rubber composition contains from0.05 phr to 10.0 phr of a soft and fast agent. In one embodiment, thesoft and fast agent is present in an amount of from 0.05 phr to 3.0 phr,or from 0.05 phr to 2.0 phr, or from 0.05 phr to 1.0 phr. In anotherembodiment, the soft and fast agent is present in an amount of from 2.0phr to 5.0 phr, or from 2.35 phr to 4.0 phr, or from 2.35 phr to 3.0phr. In an alternative high concentration embodiment, the soft and fastagent is present in an amount of from 5.0 phr to 10.0 phr, or from 6.0phr to 9.0 phr, or from 7.0 phr to 8.0 phr. In another embodiment, thesoft and fast agent is present in an amount of 2.6 phr.

Suitable soft and fast agents include, but are not limited to,organosulfur or metal-containing organosulfur compounds, an organicsulfur compound, including mono, di, and polysulfides, a thiol, ormercapto compound, an inorganic sulfide compound, a Group VIA compound,a substituted or unsubstituted aromatic organic compound that does notcontain sulfur or metal, an aromatic organometallic compound, ormixtures thereof. The soft and fast agent component may also be a blendof an organosulfur compound and an inorganic sulfide compound.

Suitable soft and fast agents of the present invention include, but arenot limited to those having the following general formula:

where R₁-R₅ can be C₁-C₈ alkyl groups; halogen groups; thiol groups(—SH), carboxylated groups; sulfonated groups; and hydrogen; in anyorder; and also pentafluorothiophenol; 2-fluorothiophenol;3-fluorothiophenol; 4-fluorothiophenol; 2,3-fluorothiophenol;2,4-fluorothiophenol; 3,4-fluorothiophenol; 3,5-fluorothiophenol2,3,4-fluorothiophenol; 3,4,5-fluorothiophenol;2,3,4,5-tetrafluorothiophenol; 2,3,5,6-tetrafluorothiophenol;4-chlorotetrafluorothiophenol; pentachlorothiophenol;2-chlorothiophenol; 3-chlorothiophenol; 4-chlorothiophenol;2,3-chlorothiophenol; 2,4-chlorothiophenol; 3,4-chlorothiophenol;3,5-chlorothiophenol; 2,3,4-chlorothiophenol; 3,4,5-chlorothiophenol;2,3,4,5-tetrachlorothiophenol; 2,3,5,6-tetrachlorothiophenol;pentabromothiophenol; 2-bromothiophenol; 3-bromothiophenol;4-bromothiophenol; 2,3-bromothiophenol; 2,4-bromothiophenol;3,4-bromothiophenol; 3,5-bromothiophenol; 2,3,4-bromothiophenol;3,4,5-bromothiophenol; 2,3,4,5-tetrabromothiophenol;2,3,5,6-tetrabromothiophenol; pentaiodothiophenol; 2-iodothiophenol;3-iodothiophenol; 4-iodothiophenol; 2,3-iodothiophenol;2,4-iodothiophenol; 3,4-iodothiophenol; 3,5-iodothiophenol;2,3,4-iodothiophenol; 3,4,5-iodothiophenol; 2,3,4,5-tetraiodothiophenol;2,3,5,6-tetraiodothiophenoland; zinc salts thereof; non-metal saltsthereof, for example, ammonium salt of pentachlorothiophenol; magnesiumpentachlorothiophenol; cobalt pentachlorothiophenol; and mixturesthereof. Preferably, the halogenated thiophenol compound ispentachlorothiophenol, which is commercially available in neat form orunder the tradename STRUKTOL®, a clay-based carrier containing thesulfur compound pentachlorothiophenol loaded at 45 percent (correlatingto 2.4 parts PCTP). STRUKTOL® is commercially available from StruktolCompany of America of Stow, Ohio. PCTP is commercially available in neatform from eChinachem of San Francisco, Calif. and in the salt form fromeChinachem of San Francisco, Calif. Most preferably, the halogenatedthiophenol compound is the zinc salt of pentachlorothiophenol, which iscommercially available from eChinachem of San Francisco, Calif.Additional examples are disclosed in U.S. Pat. No. 7,148,279, the entiredisclosure of which is hereby incorporated herein by reference.

As used herein, “organosulfur compound(s)” refers to any compoundcontaining carbon, hydrogen, and sulfur, where the sulfur is directlybonded to at least 1 carbon. As used herein, the term “sulfur compound”means a compound that is elemental sulfur, polymeric sulfur, or acombination thereof. It should be further understood that the term“elemental sulfur” refers to the ring structure of S₈ and that“polymeric sulfur” is a structure including at least one additionalsulfur relative to elemental sulfur.

Additional suitable examples of soft and fast agents include, but arenot limited to, 4,4′-diphenyl disulfide; 4,4′-ditolyl disulfide;2,2′-benzamido diphenyl disulfide; bis(2-aminophenyl)disulfide;bis(4-aminophenyl)disulfide; bis(3-aminophenyl)disulfide;2,2′-bis(4-aminonaphthyl)disulfide; 2,2′-bis(3-aminonaphthyl)disulfide;2,2′-bis(4-aminonaphthyl)disulfide; 2,2′-bis(5-aminonaphthyl)disulfide;2,2′-bis(6-aminonaphthyl)disulfide; 2,2′-bis(7-aminonaphthyl)disulfide;2,2′-bis(8-aminonaphthyl)disulfide; 1,1′-bis(2-aminonaphthyl)disulfide;1,1′-bis(3-aminonaphthyl)disulfide; 1,1′-bis(3-aminonaphthyl)disulfide;1,1′-bis(4-aminonaphthyl)disulfide; 1,1′-bis(5-aminonaphthyl)disulfide;1,1′-bis(6-aminonaphthyl)disulfide; 1,1′-bis(7-aminonaphthyl)disulfide;1,1′-bis(8-aminonaphthyl)disulfide;1,2′-diamino-1,2′-dithiodinaphthalene;2,3′-diamino-1,2′-dithiodinaphthalene; bis(4-chlorophenyl)disulfide;bis(2-chlorophenyl)disulfide; bis(3-chlorophenyl)disulfide;bis(4-bromophenyl)disulfide; bis(2-bromophenyl)disulfide;bis(3-bromophenyl)disulfide; bis(4-fluorophenyl)disulfide;bis(4-iodophenyl)disulfide; bis(2,5-dichlorophenyl)disulfide;bis(3,5-dichlorophenyl)disulfide; bis(2,4-dichlorophenyl)disulfide;bis(2,6-dichlorophenyl)disulfide; bis(2,5-dibromophenyl)disulfide;bis(3,5-dibromophenyl)disulfide; bis(2-chloro-5-bromophenyl)disulfide;bis(2,4,6-trichlorophenyl)disulfide;bis(2,3,4,5,6-pentachlorophenyl)disulfide; bis(4-cyanophenyl)disulfide;bis(2-cyanophenyl)disulfide; bis(4-nitrophenyl)disulfide;bis(2-nitrophenyl)disulfide; 2,2′-dithiobenzoic acid ethylester;2,2′-dithiobenzoic acid methylester; 2,2′-dithiobenzoic acid;4,4′-dithiobenzoic acid ethylester; bis(4-acetylphenyl)disulfide;bis(2-acetylphenyl)disulfide; bis(4-formylphenyl)disulfide;bis(4-carbamoylphenyl)disulfide; 1,1′-dinaphthyl disulfide;2,2′-dinaphthyl disulfide; 1,2′-dinaphthyl disulfide;2,2′-bis(1-chlorodinaphthyl)disulfide;2,2′-bis(1-bromonaphthyl)disulfide; 1,1′-bis(2-chloronaphthyl)disulfide;2,2′-bis(1-cyanonaphthyl)disulfide; 2,2′-bis(1-acetylnaphthyl)disulfide;and the like; or a mixture thereof. Preferred organosulfur componentsinclude 4,4′-diphenyl disulfide, 4,4′-ditolyl disulfide, or2,2′-benzamido diphenyl disulfide, or a mixture thereof. A preferredorganosulfur component includes 4,4′-ditolyl disulfide.

In another embodiment, metal-containing organosulfur components can beused according to the invention. Suitable metal-containing organosulfurcomponents include, but are not limited to, cadmium, copper, lead, andtellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate, anddimethyldithiocarbamate, or mixtures thereof. Additional examples aredisclosed in U.S. Pat. No. 7,005,479, the entire disclosure of which ishereby incorporated herein by reference.

Suitable substituted or unsubstituted aromatic organic components thatdo not include sulfur or a metal include, but are not limited to,4,4′-diphenyl acetylene, azobenzene, or a mixture thereof. The aromaticorganic group preferably ranges in size from C₆ to C₂₀, and morepreferably from C₆ to C₁₀. Suitable inorganic sulfide componentsinclude, but are not limited to titanium sulfide, manganese sulfide, andsulfide analogs of iron, calcium, cobalt, molybdenum, tungsten, copper,selenium, yttrium, zinc, tin, and bismuth.

A substituted or unsubstituted aromatic organic compound is alsosuitable as a soft and fast agent. Suitable substituted or unsubstitutedaromatic organic components include, but are not limited to, componentshaving the formula (R₁)_(x)—R₃-M-R₄—(R₂)_(y), wherein R₁ and R₂ are eachhydrogen or a substituted or unsubstituted C₁₋₂₀ linear, branched, orcyclic alkyl, alkoxy, or alkylthio group, or a single, multiple, orfused ring C₆ to C₂₄ aromatic group; x and y are each an integer from 0to 5; R₃ and R₄ are each selected from a single, multiple, or fused ringC₆ to C₂₄ aromatic group; and M includes an azo group or a metalcomponent. R₃ and R₄ are each preferably selected from a C₆ to C₁₀aromatic group, more preferably selected from phenyl, benzyl, naphthyl,benzamido, and benzothiazyl. R₁ and R₂ are each preferably selected froma substituted or unsubstituted C₁₋₁₀ linear, branched, or cyclic alkyl,alkoxy, or alkylthio group or a C₆ to C₁₀ aromatic group. When R₁, R₂,R₃, or R₄, are substituted, the substitution may include one or more ofthe following substituent groups: hydroxy and metal salts thereof;mercapto and metal salts thereof; halogen; amino, nitro, cyano, andamido; carboxyl including esters, acids, and metal salts thereof; silyl;acrylates and metal salts thereof; sulfonyl or sulfonamide; andphosphates and phosphites. When M is a metal component, it may be anysuitable elemental metal available to those of ordinary skill in theart. Typically, the metal will be a transition metal, althoughpreferably it is tellurium or selenium. In one embodiment, the aromaticorganic compound is substantially free of metal, while in anotherembodiment the aromatic organic compound is completely free of metal.

The soft and fast agent can also include a Group VIA component.Elemental sulfur and polymeric sulfur are commercially available fromElastochem, Inc. of Chardon, Ohio. Exemplary sulfur catalyst compoundsinclude PB(RM-S)-80 elemental sulfur and PB(CRST)-65 polymeric sulfur,each of which is available from Elastochem, Inc. An exemplary telluriumcatalyst under the tradename TELLOY® and an exemplary selenium catalystunder the tradename VANDEX® are each commercially available from RTVanderbilt.

Other suitable soft and fast agents include, but are not limited to,hydroquinones, benzoquinones, quinhydrones, catechols, and resorcinols.Suitable hydroquinones are further disclosed, for example, in U.S.Patent Application Publication No. 2007/0213440. Suitable benzoquinonesare further disclosed, for example, in U.S. Patent ApplicationPublication No. 2007/0213442. Suitable quinhydrones are furtherdisclosed, for example, in U.S. Patent Application Publication No.2007/0213441. Suitable catechols and resorcinols are further disclosed,for example, in U.S. Patent Application Publication No. 2007/0213144.The entire disclosure of each of these references is hereby incorporatedherein by reference.

In a particular embodiment, the soft and fast agent is a catecholselected from one or more compounds represented by the followingformula, and hydrates thereof:

-   -   wherein each R₁, R₂, R₃, and R₄, is independently selected from        the group consisting of hydrogen, a halogen group (F, Cl, Br,        I), an alkyl group, a carboxyl group (—COOH) and metal salts        thereof (e.g., —COO⁻M⁺) and esters thereof (—COOR), an acetate        group (—CH₂COOH) and esters thereof (—CH₂COOR), a formyl group        (—CHO), an acyl group (—COR), an acetyl group (—COCH₃), a        halogenated carbonyl group (—COX), a sulfo group (—SO₃H) and        esters thereof (—SO₃R), a halogenated sulfonyl group (—SO₂X), a        sulfino group (—SO₂H), an alkylsulfinyl group (—SOR), a        carbamoyl group (—CONH₂), a halogenated alkyl group, a cyano        group (—CN), an alkoxy group (—OR), a hydroxy group (—OH) and        metal salts thereof (e.g., —O⁻M⁺), an amino group (—NH₂), a        nitro group (—NO₂), an aryl group (e.g., phenyl, tolyl, etc.),        an aryloxy group (e.g., phenoxy, etc.), an arylalkyl group        [e.g., cumyl (—C(CH₃)₂phenyl); benzyl (—CH₂phenyl)], a nitroso        group (—NO), an acetamido group (—NHCOCH₃), and a vinyl group        (—CH═CH₂).

In another particular embodiment, the soft and fast agent is aresorcinol selected from one or more compounds represented by thefollowing formula, and hydrates thereof:

-   -   wherein each R₁, R₂, R₃, and R₄, is independently selected from        the group consisting of hydrogen, a halogen group (F, Cl, Br,        I), an alkyl group, a carboxyl group (—COOH) and metal salts        thereof (e.g., —COO⁻M⁺) and esters thereof (—COOR), an acetate        group (—CH₂COOH) and esters thereof (—CH₂COOR), a formyl group        (—CHO), an acyl group (—COR), an acetyl group (—COCH₃), a        halogenated carbonyl group (—COX), a sulfo group (—SO₃H) and        esters thereof (—SO₃R), a halogenated sulfonyl group (—SO₂X), a        sulfino group (—SO₂H), an alkylsulfinyl group (—SOR), a        carbamoyl group (—CONH₂), a halogenated alkyl group, a cyano        group (—CN), an alkoxy group (—OR), a hydroxy group (—OH) and        metal salts thereof (e.g., —O⁻M⁺), an amino group (—NH₂), a        nitro group (—NO₂), an aryl group (e.g., phenyl, tolyl, etc.),        an aryloxy group (e.g., phenoxy, etc.), an arylalkyl group        [e.g., cumyl (—C(CH₃)₂phenyl); benzyl (—CH₂phenyl)], a nitroso        group (—NO), an acetamido group (—NHCOCH₃), and a vinyl group        (—CH═CH₂).

The soft and fast agent may be a combination of one or more catechols,each of which is independently selected from compounds represented bythe above formula; a combination of one or more resorcinols, each ofwhich is independently selected from compounds represented by the aboveformula; a combination of at least one catechol and one or morenon-catechol soft and fast agents including, but not limited to,hydroquinones, benzoquinones, quinhydrones, and resorcinols; or acombination of at least one resorcinol and one or more non-resorcinolsoft and fast agents including, but not limited to, hydroquinones,benzoquinones, quinhydrones, and catechols.

The catechol or resorcinol is typically used in the form of a liquid orsolid. In a particular embodiment, the catechol or resorcinol is used ina solid form and may be synthesized or processed so as to have aparticle size of 0.25 mm or less, or 0.125 mm or less, or 0.09 mm orless. In another particular embodiment, the catechol or resorcinol isused in a solid form and melts at 150° F. or less, or 120° F. or less,or at a temperature that is the same as or less than the mixingtemperature of the base rubber.

When the soft and fast agent includes catechol(s) and/or resorcinol(s),the total amount of catechol(s) and/or resorcinol(s) present in therubber composition is typically at least 0.1 parts by weight or at least0.15 parts by weight or at least 0.2 parts by weight per 100 parts ofthe base rubber, or an amount within the range having a lower limit of0.1 parts or 0.15 parts or 0.25 parts or 0.3 parts or 0.375 parts byweight per 100 parts of the base rubber, and an upper limit of 0.5 partsor 1 part or 1.5 parts or 2 parts or 3 parts by weight per 100 parts ofthe base rubber.

In a particular embodiment, the soft and fast agent comprises acatechol, and a ratio (P_(CATECHOL)/P_(INITIATOR)) of the amount of thecatechol present in the rubber composition (P_(CATECHOL)) measured inparts by weight per 100 parts of the base rubber, to the amount ofinitiator agent present in the rubber composition (P_(INITIATOR)),measured in parts by weight per 100 parts of the base rubber, is from0.05 to 2. In another embodiment, P_(CATECHOL)/P_(INITIATOR) is at least0.05 and less than 0.5. In another embodiment,P_(CATECHOL)/P_(INITIATOR) is at least 0.2 and less than 0.5. In anotherembodiment, P_(CATECHOL)/P_(INITIATOR) is at least 0.25 and less than0.5. In yet another embodiment, P_(CATECHOL)/P_(INITIATOR) is within therange having a lower limit of 0.05 or 0.2 or 0.25 and an upper limit of0.4 or 0.45 or 0.5 or 2.

In another particular embodiment, the soft and fast agent comprises aresorcinol, and a ratio (P_(RESORCINOL)/P_(INITIATOR)) of the amount ofthe resorcinol present in the rubber composition (P_(RESORCINOL))measured in parts by weight per 100 parts of the base rubber, to theamount of initiator agent present in the rubber composition(P_(INITIATOR)), measured in parts by weight per 100 parts of the baserubber, is from 0.05 to 2. In another embodiment,P_(RESORCINOL)/P_(INITIATOR) is at least 0.05 and less than 0.5. Inanother embodiment, P_(RESORCINOL)/P_(INITIATOR) is at least 0.2 andless than 0.5. In another embodiment, P_(RESORCINOL)/P_(INITIATOR) is atleast 0.25 and less than 0.5. In yet another embodiment,P_(RESORCINOL)/P_(INITIATOR) is within the range having a lower limit of0.05 or 0.2 or 0.25 and an upper limit of 0.4 or 0.45 or 0.5 or 2.

Examples of commercially available polybutadienes suitable for use informing the center include, but are not limited to, Buna CB 23,commercially available from LANXESS Corporation; SE BR-1220,commercially available from The Dow Chemical Company; Europrene® NEOCIS®BR 40 and BR 60, commercially available from Polimeri Europa; UBEPOL-BR®rubbers, commercially available from UBE Industries, Ltd.; and BR 01commercially available from Japan Synthetic Rubber Co., Ltd.

Suitable types and amounts of base rubber, crosslinking agent, filler,co-crosslinking agent, initiator agent and additives are more fullydescribed in, for example, U.S. Patent Application Publication Nos.2004/0214661, 2003/0144087, and 2003/0225197, and U.S. Pat. Nos.6,566,483, 6,695,718, and 6,939,907, the entire disclosures of which arehereby incorporated herein by reference.

The center can also be formed from a low deformation material selectedfrom metal, rigid plastics, polymers reinforced with high strengthorganic or inorganic fillers or fibers, and blends and compositesthereof. Suitable low deformation materials also include those disclosedin U.S. Patent Application Publication No. 2005/0250600, the entiredisclosure of which is hereby incorporated herein by reference.

The center may also comprise thermosetting or thermoplastic materialssuch as polyurethane, polyurea, partially or fully neutralized ionomers,thermosetting polydiene rubber such as polybutadiene, polyisoprene,ethylene propylene diene monomer rubber, ethylene propylene rubber,natural rubber, balata, butyl rubber, halobutyl rubber, styrenebutadiene rubber or any styrenic block copolymer such as styreneethylene butadiene styrene rubber, etc., metallocene or other singlesite catalyzed polyolefin, polyurethane copolymers, e.g., with silicone,as long as the material meets the desired coefficient of restitution(“COR”).

The outer core layer is generally formed from a rubber composition.Suitable rubber compositions include those disclosed above.

Additional materials suitable for forming the center and outer corelayer include the core compositions disclosed in U.S. Pat. No.7,300,364, the entire disclosure of which is hereby incorporated hereinby reference. For example, suitable core materials include HNPsneutralized with organic fatty acids and salts thereof, metal cations,or a combination of both. In addition to HNPs neutralized with organicfatty acids and salts thereof, core compositions may comprise at leastone rubber material having a resilience index of at least about 40.Preferably the resilience index is at least about 50. Polymers thatproduce resilient golf balls and, therefore, are suitable for thepresent invention, include but are not limited to CB23, CB22,commercially available from of Bayer Corp. of Orange, Tex., BR60,commercially available from Enichem of Italy, and 1207G, commerciallyavailable from Goodyear Corp. of Akron, Ohio. Additionally, theunvulcanized rubber, such as polybutadiene, in golf balls preparedaccording to the invention typically has a Mooney viscosity of betweenabout 40 and about 80, more preferably, between about 45 and about 65,and most preferably, between about 45 and about 55. Mooney viscosity istypically measured according to ASTM-D1646.

The two-layer core is enclosed with a cover comprising an inner coverlayer and an outer cover layer. According to the present invention, thesurface hardness of the outer core layer is greater than the materialhardness of the inner cover layer. In a particular embodiment, thesurface hardness of the outer core layer is greater than both the innercover layer and the outer cover layer.

It should be understood that there is a fundamental difference between“material hardness” and “hardness as measured directly on a golf ball.”For purposes of the present disclosure, material hardness is measuredaccording to ASTM D2240 and generally involves measuring the hardness ofa flat “slab” or “button” formed of the material. Hardness as measureddirectly on a golf ball (or other spherical surface) typically resultsin a different hardness value. This difference in hardness values is dueto several factors including, but not limited to, ball construction(i.e., core type, number of core and/or cover layers, etc.), ball (orsphere) diameter, and the material composition of adjacent layers. Itshould also be understood that the two measurement techniques are notlinearly related and, therefore, one hardness value cannot easily becorrelated to the other. The hardness values given herein for covermaterials, including inner cover layer materials and outer cover layermaterials, are material hardness values measured according to ASTMD2240, with all values reported following 10 days of aging at 50%relative humidity and 23° C.

The inner cover layer preferably has a material hardness of 95 Shore Cor less, or less than 95 Shore C, or 92 Shore C or less, or 90 Shore Cor less, or has a material hardness within a range having a lower limitof 70 or 75 or 80 or 84 or 85 Shore C and an upper limit of 90 or 92 or95 Shore C. The thickness of the inner cover layer is preferably withina range having a lower limit of 0.010 or 0.015 or 0.020 or 0.030 inchesand an upper limit of 0.035 or 0.045 or 0.080 or 0.120 inches.

The outer cover layer preferably has a material hardness of 85 Shore Cor less. The thickness of the outer cover layer is preferably within arange having a lower limit of 0.010 or 0.015 or 0.025 inches and anupper limit of 0.035 or 0.040 or 0.055 or 0.080 inches.

Suitable materials for forming the inner and outer cover layer includeionomer resins and blends thereof (particularly Surlyn® ionomer resins),polyurethanes, polyureas, (meth)acrylic acid, thermoplastic rubberpolymers, polyethylene, and synthetic or natural vulcanized rubber, suchas balata. Suitable commercially available ionomeric cover materialsinclude, but are not limited to, Surlyn® ionomer resins and DuPont® HPF1000 and HPF 2000, commercially available from E. I. du Pont de Nemoursand Company; and Iotek® ionomers, commercially available from ExxonMobilChemical Company.

Also suitable for forming cover layers are blends of ionomers withthermoplastic elastomers. Suitable ionomeric cover materials are furtherdisclosed, for example, in U.S. Pat. Nos. 6,653,382, 6,756,436,6,894,098, 6,919,393, and 6,953,820, the entire disclosures of which arehereby incorporated by reference. Suitable polyurethane cover materialsare further disclosed in U.S. Pat. Nos. 5,334,673, 6,506,851, and6,756,436, the entire disclosures of which are hereby incorporatedherein by reference. Suitable polyurea cover materials are furtherdisclosed in U.S. Pat. Nos. 5,484,870 and 6,835,794, the entiredisclosures of which are hereby incorporated herein by reference.Suitable polyurethane-urea hybrids are blends or copolymers comprisingurethane or urea segments as disclosed in U.S. Patent ApplicationPublication No. 2007/0117923, the entire disclosure of which is herebyincorporated herein by reference. Additional suitable cover materialsare disclosed, for example, in U.S. Patent Application Publication No.2005/0164810, U.S. Pat. No. 5,919,100, and PCT Publications WO00/23519and WO00/29129, the entire disclosures of which are hereby incorporatedherein by reference.

The inner cover layer is preferably formed from a composition comprisingan ionomer or a blend of two or more ionomers. In a particularembodiment, the inner cover layer is formed from a compositioncomprising a high acid ionomer. For purposes of the present disclosure,“high acid ionomer” includes ionomers having an acid content of greaterthan 16 wt %. A particularly suitable high acid ionomer is Surlyn 8150®,commercially available from E. I. du Pont de Nemours and Company. Surlyn8150® is a copolymer of ethylene and methacrylic acid, having an acidcontent of 19 wt %, which is 45% neutralized with sodium. In anotherparticular embodiment, the inner cover layer is formed from acomposition comprising a high acid ionomer and a maleicanhydride-grafted non-ionomeric polymer. A particularly suitable maleicanhydride-grafted polymer is Fusabond 572D®, commercially available fromE. I. du Pont de Nemours and Company. Fusabond 572D® is a maleicanhydride-grafted, metallocene-catalyzed ethylene-butene copolymerhaving about 0.9 wt % maleic anhydride grafted onto the copolymer. Aparticularly preferred blend of high acid ionomer and maleicanhydride-grafted polymer is a 84 wt %/16 wt % blend of Surlyn 8150® andFusabond 572D®. Blends of high acid ionomers with maleicanhydride-grafted polymers are further disclosed, for example, in U.S.Pat. Nos. 6,992,135 and 6,677,401, the entire disclosures of which arehereby incorporated herein by reference.

In another particular embodiment, the inner cover layer is preferablyformed from a composition comprising a 50/45/5 blend of Surlyn®8940/Surlyn® 9650/Nucrel® 960, and, in a particularly preferredembodiment, has a material hardness of from 80 to 85 Shore C. In anotherparticular embodiment, the inner cover layer is preferably formed from acomposition comprising a 50/25/25 blend of Surlyn® 8940/Surlyn®9650/Surlyn® 9910, preferably having a material hardness of about 90Shore C. In yet another particular embodiment, the inner cover layer ispreferably formed from a composition comprising a 50/50 blend of Surlyn®8940/Surlyn® 9650, preferably having a material hardness of about 86Shore C. Surlyn® 8940 is an E/MAA copolymer in which the MAA acid groupshave been partially neutralized with sodium ions. Surlyn® 9650 andSurlyn® 9910 are two different grades of E/MAA copolymer in which theMAA acid groups have been partially neutralized with zinc ions. Nucrel®960 is an E/MAA copolymer resin nominally made with 15 wt % methacrylicacid. Surlyn® 8940, Surlyn® 9650, Surlyn® 9910, and Nucrel® 960 arecommercially available from E. I. du Pont de Nemours and Company.

Non-limiting examples of preferred inner cover layer materials are shownin the Examples below.

Ionomeric compositions of the present invention can be blended withnon-ionic thermoplastic resins, particularly to manipulate productproperties. Examples of suitable non-ionic thermoplastic resins include,but are not limited to, polyurethane, poly-ether-ester,poly-amide-ether, polyether-urea, Pebax® thermoplastic polyether blockamides commercially available from Arkema Inc.,styrene-butadiene-styrene block copolymers,styrene(ethylene-butylene)-styrene block copolymers, polyamides,polyesters, polyolefins (e.g., polyethylene, polypropylene,ethylene-propylene copolymers, ethylene-(meth)acrylate,ethylene-(meth)acrylic acid, functionalized polymers with maleicanhydride grafting, Fusabond® functionalized olefins commerciallyavailable from E. I. du Pont de Nemours and Company, functionalizedpolymers with epoxidation, elastomers (e.g., EPDM, metallocene-catalyzedpolyethylene) and ground powders of the thermoset elastomers.

The inner cover layer material may include a flow modifier, such as, butnot limited to, Nucrel® acid copolymer resins, and particularly Nucrel®960. Nucrel® acid copolymer resins are commercially available from E. I.du Pont de Nemours and Company.

The outer cover layer is preferably formed from a composition comprisingpolyurethane, polyurea, or a copolymer or hybrid ofpolyurethane/polyurea. The outer cover layer material may bethermoplastic or thermoset.

In a particularly preferred embodiment, the present invention provides agolf ball consisting of: a center, an outer core layer, an inner coverlayer, and an outer cover layer. The center is preferably formed from arubber composition and, in a particularly preferred embodiment, has oneor more of the following properties: a diameter of about 1.00 inches, acompression of about 30, a center hardness of about 60 Shore C, and asurface hardness of about 75 Shore C. The rubber composition of thecenter preferably has the following formulation: 100 parts high-cisbutadiene rubber, 22 phr zinc diacrylate, 5 phr zinc oxide, BaSO₄ inamount necessary to achieve the desired specific gravity, 0.5 phr zincpentachlorothiophenol, 1.2 phr Perkadox BC, and from 10 to 20 phrregrind material. The outer core is preferably formed from a rubbercomposition preferably having the following formulation: 93 partshigh-cis butadiene rubber, 7 parts polyisoprene, 33-39 phr zincdiacrylate, zinc oxide in amount necessary to achieve the desiredspecific gravity, 0.5 phr zinc pentachlorothiophenol, 1.2 phr PerkadoxBC, 0.4 phr MBPC antioxidant, and 10-20 phr regrind material. Theoverall two-layer core preferably has one or more of the followingproperties: an overall diameter of about 1.53 inches, a dual corecompression of about 80, an outer core layer surface hardness of about89 Shore C, and a core hardness gradient of about 29 Shore C. The innercover layer is preferably formed from a composition comprising a 84 wt%/16 wt % blend of Surlyn 8150® and Fusabond 572D®. The inner coverlayer preferably has a material hardness of from 85 to 92 Shore C. Theouter cover layer is preferably formed from a polyurethane or polyureacomposition.

A moisture vapor barrier layer is optionally employed between the coreand the cover. Moisture vapor barrier layers are further disclosed, forexample, in U.S. Pat. Nos. 6,632,147, 6,932,720, 7,004,854, and7,182,702, the entire disclosures of which are hereby incorporatedherein by reference.

In addition to the materials disclosed above, any of the core or coverlayers may comprise one or more of the following materials:thermoplastic elastomer, thermoset elastomer, synthetic rubber,thermoplastic vulcanizate, copolymeric ionomer, terpolymeric ionomer,polycarbonate, polyolefin, polyamide, copolymeric polyamide, polyesters,polyester-amides, polyether-amides, polyvinyl alcohols,acrylonitrile-butadiene-styrene copolymers, polyarylate, polyacrylate,polyphenylene ether, impact-modified polyphenylene ether, high impactpolystyrene, diallyl phthalate polymer, metallocene-catalyzed polymers,styrene-acrylonitrile (SAN), olefin-modified SAN,acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-diene rubber(EPDM), ethylene-vinyl acetate copolymer (EVA), ethylene propylenerubber (EPR), ethylene vinyl acetate, polyurea, and polysiloxane.Suitable polyamides for use as an additional material in compositionsdisclosed herein also include resins obtained by: (1) polycondensationof (a) a dicarboxylic acid, such as oxalic acid, adipic acid, sebacicacid, terephthalic acid, isophthalic acid or 1,4-cyclohexanedicarboxylicacid, with (b) a diamine, such as ethylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ordecamethylenediamine, 1,4-cyclohexyldiamine or m-xylylenediamine; (2) aring-opening polymerization of cyclic lactam, such as ε-caprolactam orω-laurolactam; (3) polycondensation of an aminocarboxylic acid, such as6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or12-aminododecanoic acid; or (4) copolymerization of a cyclic lactam witha dicarboxylic acid and a diamine. Specific examples of suitablepolyamides include Nylon 6, Nylon 66, Nylon 610, Nylon 11, Nylon 12,copolymerized Nylon, Nylon MXD6, and Nylon 46.

Other preferred materials suitable for use as an additional material ingolf ball compositions disclosed herein include Skypel polyesterelastomers, commercially available from SK Chemicals of South Korea;Septon® diblock and triblock copolymers, commercially available fromKuraray Corporation of Kurashiki, Japan; and Kraton® diblock andtriblock copolymers, commercially available from Kraton Polymers LLC ofHouston, Tex.

Ionomers are also well suited for blending with compositions disclosedherein. Suitable ionomeric polymers include α-olefin/unsaturatedcarboxylic acid copolymer- or terpolymer-type ionomeric resins.Copolymeric ionomers are obtained by neutralizing at least a portion ofthe carboxylic groups in a copolymer of an α-olefin and anα,β-unsaturated carboxylic acid having from 3 to 8 carbon atoms, with ametal ion. Terpolymeric ionomers are obtained by neutralizing at least aportion of the carboxylic groups in a terpolymer of an α-olefin, anα,β-unsaturated carboxylic acid having from 3 to 8 carbon atoms, and anα,β-unsaturated carboxylate having from 2 to 22 carbon atoms, with ametal ion. Examples of suitable α-olefins for copolymeric andterpolymeric ionomers include ethylene, propylene, 1-butene, and1-hexene. Examples of suitable unsaturated carboxylic acids forcopolymeric and terpolymeric ionomers include acrylic, methacrylic,ethacrylic, α-chloroacrylic, crotonic, maleic, fumaric, and itaconicacid. Copolymeric and terpolymeric ionomers include ionomers havingvaried acid contents and degrees of acid neutralization, neutralized bymonovalent or bivalent cations as disclosed herein. Examples ofcommercially available ionomers suitable for blending with compositionsdisclosed herein include Surlyn® ionomer resins, commercially availablefrom E. I. du Pont de Nemours and Company, and Iotek® ionomers,commercially available from ExxonMobil Chemical Company.

Silicone materials are also well suited for blending with compositionsdisclosed herein. Suitable silicone materials include monomers,oligomers, prepolymers, and polymers, with or without adding reinforcingfiller. One type of silicone material that is suitable can incorporateat least 1 alkenyl group having at least 2 carbon atoms in theirmolecules. Examples of these alkenyl groups include, but are not limitedto, vinyl, allyl, butenyl, pentenyl, hexenyl, and decenyl. The alkenylfunctionality can be located at any location of the silicone structure,including one or both terminals of the structure. The remaining (i.e.,non-alkenyl) silicon-bonded organic groups in this component areindependently selected from hydrocarbon or halogenated hydrocarbongroups that contain no aliphatic unsaturation. Non-limiting examples ofthese include: alkyl groups, such as methyl, ethyl, propyl, butyl,pentyl, and hexyl; cycloalkyl groups, such as cyclohexyl andcycloheptyl; aryl groups, such as phenyl, tolyl, and xylyl; aralkylgroups, such as benzyl and phenethyl; and halogenated alkyl groups, suchas 3,3,3-trifluoropropyl and chloromethyl. Another type of suitablesilicone material is one having hydrocarbon groups that lack aliphaticunsaturation. Specific examples include: trimethylsiloxy-endblockeddimethylsiloxane-methylhexenylsiloxane copolymers;dimethylhexenylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxanecopolymers; trimethylsiloxy-endblockeddimethylsiloxane-methylvinylsiloxane copolymers;trimethylsiloxyl-endblockedmethylphenylsiloxane-dimethylsiloxane-methylvinysiloxane copolymers;dimethylvinylsiloxy-endblocked dimethylpolysiloxanes;dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxanecopolymers; dimethylvinylsiloxy-endblocked methylphenylpolysiloxanes;dimethylvinylsiloxy-endblockedmethylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers;and the copolymers listed above wherein at least one group isdimethylhydroxysiloxy. Examples of commercially available siliconessuitable for blending with compositions disclosed herein includeSilastic® silicone rubber, commercially available from Dow CorningCorporation of Midland, Mich.; Blensil® silicone rubber, commerciallyavailable from General Electric Company of Waterford, N.Y.; andElastosil® silicones, commercially available from Wacker Chemie AG ofGermany.

Other types of copolymers can also be added to the golf ballcompositions disclosed herein. For example, suitable copolymerscomprising epoxy monomers include styrene-butadiene-styrene blockcopolymers in which the polybutadiene block contains an epoxy group, andstyrene-isoprene-styrene block copolymers in which the polyisopreneblock contains epoxy. Examples of commercially available epoxyfunctionalized copolymers include ESBS A1005, ESBS A1010, ESBS A1020,ESBS AT018, and ESBS AT019 epoxidized styrene-butadiene-styrene blockcopolymers, commercially available from Daicel Chemical Industries, Ltd.of Japan.

Ionomeric compositions used to form golf ball layers of the presentinvention can be blended with non-ionic thermoplastic resins,particularly to manipulate product properties. Examples of suitablenon-ionic thermoplastic resins include, but are not limited to,polyurethane, poly-ether-ester, poly-amide-ether, polyether-urea, Pebax®thermoplastic polyether block amides commercially available from ArkemaInc., styrene-butadiene-styrene block copolymers,styrene(ethylene-butylene)-styrene block copolymers, polyamides,polyesters, polyolefins (e.g., polyethylene, polypropylene,ethylene-propylene copolymers, ethylene-(meth)acrylate,ethylene-(meth)acrylic acid, functionalized polymers with maleicanhydride grafting, epoxidation, etc., elastomers (e.g., EPDM,metallocene-catalyzed polyethylene) and ground powders of the thermosetelastomers.

Also suitable for forming the core are the compositions having high CORwhen formed into solid spheres disclosed in U.S. Patent ApplicationPublication No. 2003/0130434 and U.S. Pat. No. 6,653,382, the entiredisclosures of which are hereby incorporated herein by reference.

The present invention is not limited by any particular process forforming the golf ball layer(s). It should be understood that thelayer(s) can be formed by any suitable technique, including injectionmolding, compression molding, casting, and reaction injection molding.

Golf balls of the present invention typically have a coefficient ofrestitution of 0.70 or greater, preferably 0.75 or greater, and morepreferably 0.78 or greater. Golf balls of the present inventiontypically have a compression of 40 or greater, or a compression within arange having a lower limit of 50 or 60 and an upper limit of 100 or 120.Cured polybutadiene-based compositions suitable for use in golf balls ofthe present invention typically have a hardness of 15 Shore A orgreater, and preferably have a hardness of from 30 Shore A to 80 ShoreD, more preferably from 50 Shore A to 60 Shore D.

Golf balls of the present invention will typically have dimple coverageof 60% or greater, preferably 65% or greater, and more preferably 75% orgreater.

The United States Golf Association specifications limit the minimum sizeof a competition golf ball to 1.680 inches. There is no specification asto the maximum diameter, and golf balls of any size can be used forrecreational play. Golf balls of the present invention can have anoverall diameter of any size. The preferred diameter of the present golfballs is from 1.680 inches to 1.800 inches. More preferably, the presentgolf balls have an overall diameter of from 1.680 inches to 1.760inches, and even more preferably from 1.680 inches to 1.740 inches.

Golf balls of the present invention preferably have a moment of inertia(“MOT”) of 70-95 g·cm², preferably 75-93 g·cm², and more preferably76-90 g·cm². For low MOT embodiments, the golf ball preferably has anMOT of 85 g·cm² or less, or 83 g·cm² or less. For high MOT embodiment,the golf ball preferably has an MOT of 86 g·cm² or greater, or 87 g·cm²or greater. MOT is measured on a model MOI-005-104 Moment of InertiaInstrument manufactured by Inertia Dynamics of Collinsville, Conn. Theinstrument is connected to a PC for communication via a COMM port and isdriven by MOT Instrument Software version #1.2.

Golf ball cores of the present invention preferably have an overalldual-core compression of from 75 to 90, or from 60 to 85, or acompression of about 80. Golf ball centers of the present inventionpreferably have a compression of 40 or less, or from 20 to 40, or acompression of about 30.

Compression is an important factor in golf ball design. For example, thecompression of the core can affect the ball's spin rate off the driverand the feel. As disclosed in Jeff Dalton's Compression by Any OtherName, Science and Golf IV, Proceedings of the World Scientific Congressof Golf (Eric Thain ed., Routledge, 2002) (“J. Dalton”), severaldifferent methods can be used to measure compression, including Atticompression, Riehle compression, load/deflection measurements at avariety of fixed loads and offsets, and effective modulus. For purposesof the present invention, “compression” refers to Atti compression andis measured according to a known procedure, using an Atti compressiontest device, wherein a piston is used to compress a ball against aspring. The travel of the piston is fixed and the deflection of thespring is measured. The measurement of the deflection of the spring doesnot begin with its contact with the ball; rather, there is an offset ofapproximately the first 1.25 mm (0.05 inches) of the spring'sdeflection. Very low stiffness cores will not cause the spring todeflect by more than 1.25 mm and therefore have a zero compressionmeasurement. The Atti compression tester is designed to measure objectshaving a diameter of 42.7 mm (1.68 inches); thus, smaller objects, suchas golf ball cores, must be shimmed to a total height of 42.7 mm toobtain an accurate reading. Conversion from Atti compression to Riehle(cores), Riehle (balls), 100 kg deflection, 130-10 kg deflection oreffective modulus can be carried out according to the formulas given inJ. Dalton.

Golf ball cores of the present invention preferably have a zero orpositive hardness gradient. The hardness gradient is defined by hardnessmeasurements made at the surface of the inner core (or outer core layer)and radially inward towards the center of the inner core, typically at 2mm increments. For purposes of the present invention, the term“positive” with respect to the hardness gradient refers to the result ofsubtracting the hardness value at the innermost portion of the golf ballcomponent from the hardness value at the outer surface of the component.For example, if the outer surface of a solid core has a higher hardnessvalue than the center (i.e., the surface is harder than the center), thehardness gradient will be deemed a “positive” gradient. Hardnessgradients are measured by preparing the core according to the proceduregiven above for measuring the center hardness of the core. Hardnessmeasurements at any distance from the center of the core are thenmeasured by drawing a line radially outward from the center mark, andmeasuring and marking the distance from the center, typically in 2 mmincrements. All hardness measurements performed on a plane passingthrough the geometric center are performed while the core is still inthe holder and without having disturbed its orientation, such that thetest surface is constantly parallel to the bottom of the holder. Thehardness difference from any predetermined location on the core iscalculated as the average surface hardness minus the hardness at theappropriate reference point, e.g., at the center of the core for asingle, solid core, such that a core surface softer than its center willhave a negative hardness gradient and a core surface harder than itscenter will have a positive hardness gradient. Hardness gradients aredisclosed more fully, for example, in U.S. patent application Ser. No.11/832,163, filed on Aug. 1, 2007, the entire disclosure of which ishereby incorporated herein by reference.

EXAMPLES

It should be understood that the examples below are for illustrativepurposes only. In no manner is the present invention limited to thespecific disclosures therein.

Twelve ionomeric inner cover layer compositions according to the presentinvention were prepared by melt blending Surlyn® 8150 and Fusabond® 572Din a twin screw extruder, at a temperature of at least 450° F. (230°C.). The relative amounts of each component used are indicated in Table1.

Flex bars of each blend composition were formed and evaluated forhardness according to ASTM D2240 following 10 days of aging at 50%relative humidity and 23° C. The results are reported in Table 1.

TABLE 1 Fusabond ® Shore C Surlyn ® 8150, 572D, Hardness at Example wt %wt % 10 Days 1 89 11 91.2 2 84 16 89.8 3 84 16 90.4 4 84 16 89.6 5 81 1988.9 6 80 20 89.1 7 78 22 88.1 8 76 24 87.6 9 76 24 87.2 10 73 27 86.611 71 29 86.7 12 67 33 84.0

When numerical lower limits and numerical upper limits are set forthherein, it is contemplated that any combination of these values may beused.

All patents, publications, test procedures, and other references citedherein, including priority documents, are fully incorporated byreference to the extent such disclosure is not inconsistent with thisinvention and for all jurisdictions in which such incorporation ispermitted.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by those ofordinary skill in the art without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the scope of theclaims appended hereto be limited to the examples and descriptions setforth herein, but rather that the claims be construed as encompassingall of the features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those of ordinary skill in the art to which the inventionpertains.

What is claimed is:
 1. A golf ball consisting essentially of: a centerformed from a first rubber composition and having a diameter of from0.75 inches to 1.19 inches, a center hardness of from 60 Shore C to 70Shore C, a surface hardness of from 75 Shore C to 85 Shore C, and acompression of from 20 to 40; an outer core layer formed from a secondrubber composition and having a surface hardness of 80 Shore C orgreater; an inner cover layer formed from a thermoplastic compositionand having a material hardness of less than 95 Shore C; and an outercover layer formed from a thermosetting polyurethane or polyureacomposition; wherein the surface hardness of the center is at least 10Shore C units greater than the center hardness; wherein the surfacehardness of the outer core layer is at least 20 Shore C units greaterthan the center hardness; and wherein the surface hardness of the outercore layer is greater than the material hardness of the inner coverlayer.
 2. The golf ball of claim 1, wherein the diameter of the centeris from 0.85 inches to 1.15 inches.
 3. The golf ball of claim 1, whereinthe diameter of the center is from 0.875 inches to 1.125 inches.
 4. Thegolf ball of claim 1, wherein the surface hardness of the outer corelayer is greater than the material hardness of the outer cover layer. 5.The golf ball of claim 1, wherein the material hardness of the innercover layer is from 80 Shore C to 95 Shore C.
 6. The golf ball of claim1, wherein the material hardness of the inner cover layer is from 84Shore C to 92 Shore C.
 7. The golf ball of claim 1, wherein the surfacehardness of the outer core layer is at least 25 Shore C units greaterthan the center hardness.